Thread wound golf ball

Abstract: Disclosed is a thread wound golf ball wherein deterioration of performances due to bleeding of an oily substance contained in a solid rubber having a crosslinked structure as a center prevented. The thread wound golf ball comprises a solid center, a thread rubber layer provided on the outside of the solid center and a cover for covering the thread rubber layer, wherein solid center is composed of an inner rubber portion and an oil-resistant substance covering the inner rubber portion, and inner rubber portion has a crosslinked rubber structure and contain an oily substance, whereby bleeding of the oily substance is prevented.

Description: The present invention relates to a thread wound golf ball. A thread wound golf ball is obtained by winding thread rubber on a solid or liquid rubber center to form a thread rubber layer and coating the outside of the thread rubber layer with a cover material (e.g. ionomer, balata, etc.). As the solid rubber center, a vulcanized butadiene rubber has been used in the prior art. This has a considerably high hardness and small compression strain. Golf balls with such a center have high spin and a low launch angle resulting in disadvantageous flight distance. Further, the golf ball sometimes turns too much when the ball is hit. On the other hand, a liquid center has a high compression strain. Golf balls with such a liquid center, have low spin and a high launch angle, resulting in advantageous flight distance in comparison with golf balls having a conventional solid center. However, the production process of liquid centers is complicated and, further, liquid from liquid centers may splash out when the golf ball is cut by a cutter, which may result in the loss of eyesight. The present inventors have found that, by using solid rubber having a crosslinked structure containing an oily substance as the center of the thread wound golf ball, the spin is reduced and launch angle is increased under proper initial velocity, thereby improving the flight distance of the golf ball. This applies for both wood and iron shots with good balance (Japanese Patent Application No. 4-149304). However, the oily substance of the center has been found to bleed over time and to penetrate into the thread rubber layer, which results in deterioration of impact resilience. Accordingly, performances of the golf ball could not be maintained. GB-16,288 relates to a thread wound golf ball as described in the preamble of claim 1. It has now been found that, by coating the outside of the solid rubber center containing the oily substance with an oil-resistant substance, bleeding can be prevented to maintain performances of the golf ball. The main object of the present invention is to provide a thread wound golf ball wherein deterioration of performance due to bleeding of the oily substance contained in a solid rubber center having a crosslinked structure is prevented. This object as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following description. The present invention provides a thread wound golf ball comprising a solid center, a thread rubber layer provided on the outside of the solid center and a cover for covering the thread rubber layer, wherein said solid center is composed of an inner rubber portion and an oil-resistant substance covering the inner rubber portion, and said inner rubber portion has a crosslinked rubber structure and contain an oily substance. Bleeding of the oily substance of the inner rubber portion is thus prevented. The base rubber for obtaining the inner rubber center may be any one which can be vulcanized with sulphur or peroxide, for example, there can be suitably used polybutadiene rubber (BR), natural rubber (NR), ethylene-propylene-diene monomer terpolymer rubber (EPDM) or polynorbornene rubber Further, styrene, ethylene or urethane thermoplastic rubbers can also be used. In any case, it is desired that the rubber has superior compatibility with a specific oily substance that it comprises as much as possible of the oily substance, and that the rubber has suitable impact resilience when a crosslinked structure is formed with the oily substance uniformly dispersed therein. The oily substance may be any one which exhibits fluidity or semi-solid form at room temperature and has low volatility. Particularly, an oily substance which has superior compatibility with the above rubber and which causes little deterioration of impact resilience thereof when uniformly dispersed therein, or an oily substance which can impart suitable impact resilience to a rubber having low impact resilience by mixing with the rubber is preferred. Examples of the oily substance include the following: (1) Petroleum compounded oil: this is normally used as an extender oil and is classified into the following according to the content of aromatic rings, naphthene rings or paraffin chain; (i) Paraffinic oil: It contains not less than 50% of paraffin chain. (ii) Naphthenic oil: It contains 30 to 45% of naphthenic ring carbon. (iii) Aromatic oil: It contains not less than 35% of aromatic ring carbon. (2) Plasticizer Examples thereof include phthalate plasticizer such as DBP(dibutyl phthalate), DOP(dioctyl phthalate), etc.; adipate plasticizer such as DOA(dioctyl adipate), etc.; sebacate plasticizer such as DOS(dioctyl sebacate), etc.; phosphate plasticizer such as TCP(tricresyl phosphate), etc.; and adipic acid plasticizer. (3) Rubber substitute (factice): This is obtained by vulcanizing a vegetable oil with sulphur- or sulphur chloride and examples thereof include candy substitute, black substitute, and brown substitute. (4) Alkylbenzene: Examples thereof include 1-dodecyl-4-hexylbenzene, 1-dodecyl-3-hexylbenzene, 1.3.5-methylene, and 1.2.3-hemimellitene. (5) Liquid rubber: Examples thereof include liquid polybutadiene, and liquid polyisoprene. These oily substances may be used alone or in combination of one or more thereof. The combination of the oily substance and base rubber is selected by taking the compatibility of the oily substance with the rubber into consideration. Typical examples of suitable combinations include polybutadiene or natural rubber/naphthenic oil or aromatic oil; EPDM/paraffinic oil; polynorbornene rubber/naphthenic oil, aromatic oil, plasticizer, alkylbenzene or paraffinic oil; urethane rubber/plasticizer or rubber substitute The amount of the oily substance is preferably in the range of from 30 to 500 parts by weight, more preferably in the range of from 50 to 400 parts by weight, based on 100 parts by weight of the rubber. When the amount is smaller than about 30 parts by weight, no improvement effect is obtained. On the other hand, when the amount is larger than about 500 parts by weight, the oil can not be mixed with the rubber in case of a specific combination. If necessary, fillers as specific gravity adjustors (e.g. barium sulfate, etc.), reinforcers (e.g. water-containing silicic acid, carbon black, etc.), processing aids as tackifiers, antioxidants, etc. can be added to the inner rubber center, in addition to the base rubber and oily substance. When the sulphur vulcanization is conducted, sulphur, zinc oxide, stearic acid, vulcanization accelerator, zinc stearate, etc. are added as a vulcanization agent and, when the peroxide vulcanization is conducted, organic peroxide (e.g. dicumyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, etc.), activator (e.g. zinc stearate, etc.), zinc oxide, co-crosslinking agent (e.g. zinc acrylate, zinc methacrylate, N,N'-m-phenylene dimaleimide, etc.), etc. are added in a suitable amount to give a vulcanizable rubber composition. In the present invention, the above-described inner rubber center is coated with a specific material to form a solid center. The material for coating the inner rubber center part may be any one which prevents bleeding of the oily substance contained within the inner rubber center. There can normally be used an oil-resistant substance having flexibility, such as thermoplastic resin, or an oil-resistant rubber. Typical examples thereof include ionomer resin, NBR, chloroprene rubber, urethane rubber or fluorosilicone rubber. However, it is necessary to use them without deterioration of physical properties of the inner rubber center. A thickness of the oil-resistant substance is not specifically limited, but it is preferably in the range of from 0.01 to 5mm, more preferably in the range of 0.1 to 2mm. In the present invention, the inner rubber composition is molded in a die in advance perhaps by a compression molding, or injection molding. Thereafter, the resulting inner center is coated with an oil-resistant substance and subjected to a compression molding or injection molding to obtain a solid center having a predetermined size. Then, thread rubber (for a golf ball)is wound on the resulting center to form a thread wound center comprising a center and a thread rubber layer, on which a half-shell of a cover material comprising an ionomer resin or balata (transpolyisoprene) as a main component is coated, followed by molding in a die provided with dimples to obtain the desired golf ball. If the solid center obtained according to the present invention does not have suitable impact resilience, when the ball is hit it has a low initial velocity, which results in small flight distance. When the impact resilience of the solid center is represented by the height of the rebound obtained by dropping the solid center on a rigid plane such as concrete block from the height of 254 cm (100 in.) at 23°C, the value of the height is preferably not more than 70 cm. When the value is smaller than 70 cm, the initial velocity of the golf ball becomes too low, and it becomes difficult to enable the solid center to exhibit the effect thereof. It is necessary that the strain on loading of 500 g weight of the solid center is preferably not less than 0.5 mm, more preferably 1 to 5 mm. When the strain is smaller than the above range, the spin of the base when hit becomes large and, at the same time, the shot feel becomes inferior. Further, the outer diameter of the solid center is normally in the range of from 23 to 34mm, preferably in the range of from 26 to 32mm. When the outer diameter is smaller than 23mm, the spin of the ball becomes high and the launch angle becomes low. On the other hand, when the outer diameter is larger than 34mm, the thread rubber layer becomes thin and the predetermined hardness of the golf ball is not obtained. According to the present invention, bleeding of the oily substance contained in the solid center is prevented, thereby causing no deterioration of performances of the golf ball. Further, an excellent golf ball wherein the effect obtained by formulating the oily substance in the inner rubber center (e.g. reduction of spin, improvement of balance of flying distance in case of wood or iron shot, etc.) is maintained can be obtained. The following Examples and Comparative Examples further illustrate the present invention in detail Examples 1 to 4 and Comparative Examples 1 to 3 Each formulation shown in Table 1 was subjected to compression molding/vulcanization at 155°C for 20 minutes to form an inner rubber center, respectively. Then, the rubber centers (Examples 1 and 3) and rubber center (Example 2) were coated with an ionomer resin of 0.1 mm in thickness and an ionomer resin of 0.2 mm in thickness, respectively, and then subjected to compression molding to obtain solid centers. Further, the rubber center of Example 4 was coated with a non-vulcanized rubber comprising a formulation shown in Table 2 (thickness: 1 mm), and then subjected to compression molding/vulcanization to obtain a center. Then, a thread wound golf ball with an ionomer cover was produced using the resulting center. The initial flying performances and the flying performances after 6 months of the resulting golf ball were evaluated by a normal method. The results are shown in Table 3. Example No. Comparative Example No. 1 2 3 4 1 2 3 Norsolex 100 100 100 100 - 100 100 Sansen 255ZJ 200 200 300 200 - 200 300 BR11 - - - - 100 - - Sulphur 2 2 2 2 10 2 2 Zinc white 5 5 5 5 5 5 5 Stearic acid 2 2 2 2 2 2 2 Barium sulfate 245 255 330 280 75 240 320 Noxxelar CZ - - - - 1.5 - - Noxxelar TT 0.8 0.8 0.8 0.8 0.2 0.8 0.8 Noxxelar M 0.8 0.8 0.8 0.8 - 0.8 0.8 Noxxelar TBT-N 1.2 1.2 1.2 1.2 - 1.2 1.2 Sanselar TE-G 0.4 0.4 0.4 0.4 - 0.4 0.4 N230S 100 Zinc oxide 5 Stearic acid 1.5 FEF Black 20 FT Black 30 DOP 10 Antioxidant OD 1.5 Vulcanization accelerator CZ 1.5 Sulphur 0.3 Example No. Comparative Example No. 1 2 3 4 1 2 3 Ball center Inner center (mm) 30.0 30.0 30.0 28.2 30.0 30.0 30.0 Outer diameter (mm) 30.2 30.4 30.2 30.2 30.0 30.0 30.0 Weight (g) 20.9 20.5 20.3 20.4 20.5 20.5 20.4 Compression strain (mm) 1.3 1.1 2.5 1.7 0.4 1.5 2.7 Impact resilience (cm) 110 105 107 95 215 125 120 Ball Weight (g) 45.5 45.3 45.2 45.3 45.4 45.3 45.4 Compression Beginning 78 78 77 79 78 78 79 After 6 months 78 78 77 79 78 75 75 Flying performances 1 Launch angle (°) Beginning 11.6 11.4 11.8 11.5 10.5 11.8 12.0 After 6 months 11.7 11.4 11.8 11.6 10.6 10.8 11.1 Spin (rpm) Beginning 3150 3180 3100 3150 3300 3050 2950 After 6 months 3150 3200 3050 3100 3400 3300 3250 Carry (yard) Beginning 224.5 223.5 223.0 222.0 218.5 224.5 224.0 After 6 months 224.0 223.5 223.5 223.0 218.0 220.5 220.0 Total (yard) Beginning 228.0 225.5 226.0 225.5 221.5 228.5 228.0 After 6 months 228.5 227.5 227.5 226.0 221.0 223.5 224.0 Flying performances 2 Launch angle (°) Beginning 14.8 14.6 15.1 14.8 14.1 15.0 15.2 After 6 months 15.1 14.7 15.2 14.8 14.3 13.9 14.0 Spin (rpm) Beginning 3920 4000 3950 4010 4400 3900 3850 After 6 months 4010 4150 3990 4000 4500 4300 4350 Carry (yard) Beginning 178.0 176.5 176.0 175.0 172.0 178.0 177.5 After 6 months 177.5 176.5 176.0 174.0 171.0 173.5 173.0 Total (yard) Beginning 185.0 184.0 184.0 183.0 179.0 185.0 184.0 After 6 months 184.0 183.0 184.5 182.0 178.0 181.0 180.0 Examples 5 to 8 and Comparative Examples 4 to 6 Each formulation shown in Table 4 was subjected to compression molding/vulcanization at 155°C for 20 minutes to form an inner rubber center, respectively Then, the rubber centers (Examples 5 and 7) and rubber center (Example 6) were coated with an ionomer resin of 0.1 mm in thickness and an ionomer resin of 0.2 mm in thickness, respectively, and then subjected to compression molding to obtain solid centers. Further, the rubber center of Example 8 was coated with a non-vulcanized rubber comprising a formulation shown in Table 2 (thickness: 1 mm), and then subjected to compression molding/vulcanisation to obtain a center. Then, a thread wound golf ball with a balata cover was produced using the resulting center. The initial flying performances and the flying performances after 6 months of the resulting golf ball were evaluated by a normal method. The results are shown in Table 5. Example No. Comparative Example No. 5 6 7 8 4 5 6 Norsolex 100 100 100 100 - 100 100 Sansen 255ZJ 200 200 300 200 - 200 300 BR11 - - - - 100 - - Sulphur 2 2 2 2 10 2 2 Zinc white 5 5 5 5 5 5 5 Stearic acid 2 2 2 2 2 2 2 Barium sulfate 215 220 290 250 95 210 280 Noxxelar CZ - - - - 1.5 - - Noxxelar TT 0.8 0.8 0.8 0.8 0.2 0.8 0.8 Noxxelar M 0.8 0.8 0.8 0.8 - 0.8 0.8 Noxxelar TBT-N 1.2 1.2 1.2 1.2 - 1.2 1.2 Sanselar TE-G 0.4 0.4 0.4 0.4 - 0.4 0.4 Example No. Comparative Example No. 5 6 7 8 4 5 6 Ball center Inner center (mm) 28.2 28.2 28.2 26.4 28.2 28.2 28.2 Outer diameter (mm) 28.4 28.6 28.4 28.4 28.2 28.2 28.2 Weight (g) 17.1 17.1 17.2 17.1 17.1 17.1 17.0 Compression strain (mm) 1.2 1.0 2.4 1.7 0.4 1.4 2.5 Impact resilience (cm) 110 103 106 96 215 125 120 Ball Weight (g) 45.5 45.3 45.2 45.3 45.4 45.3 45.4 Compression Beginning 90 90 90 90 90 90 90 After 6 months 90 90 90 90 90 87 86 Flying performances 1 Launch angle (°) Beginning 10.8 10.6 11.0 11.1 9.5 11.2 11.3 After 6 months 10.8 10.7 11.1 11.2 9.6 10.5 10.3 Spin (rpm) Beginning 3450 3500 3420 3400 3900 3400 3380 After 6 months 3500 3580 3460 3450 3980 3750 3700 Carry (yard) Beginning 216 216.5 216.5 217.0 210 216.0 216.5 After 6 months 217 216.5 217.0 217.5 211 214.0 213.5 Total (yard) Beginning 223 223.0 223.5 224.0 214 223.0 223.0 After 6 months 224.5 224.0 224.0 224.5 215 220.0 219.5 Flying performances 2 Launch angle (°) Beginning 13.5 13.3 13.8 13.6 12.5 13.8 13.9 After 6 months 13.7 13.4 13.9 13.7 12.4 13.0 12.8 Spin (rpm) Beginning 4500 4600 4450 4550 5500 4550 4480 After 6 months 4450 4540 4420 4470 5400 4850 4900 Carry (yard) Beginning 172 171.5 172.0 172.0 165 171.5 172.0 After 6 months 172.5 172.0 173.0 171.5 166.0 168.5 169.5 Total (yard) Beginning 177 176.0 176.5 177.0 168 176.0 176.0 After 6 months 176.5 176.0 177.0 177.5 167.5 173.5 174.0 As is apparent from the above results, the golf ball having the inner rubber center containing the oily substance among both golf balls with ionomer cover and those with the balata cover, had improved flight distance due to high launch angle and low spin. Further, the golf balls of Comparative Examples 2, 3, 5 and 6, had compression values after 6 months of 3 to 5 points lower than the initial compression, and the launch angle became low and the spin became high. On the other hand, in the golf balls of Examples 1 to 4 and 5 to 8, no change was observed in the compression, and no change was observed in either launch angle or spin in comparison with initial performances. Further, feeling and control properties were confirmed according to a practical hitting test by a professional golfer. As a result, it is evaluated that all of the golf balls of the above Examples have excellent shot feel and control properties.

Claims: A thread wound golf ball comprising a solid center, which comprises an inner rubber portion having a crosslinked rubber structure, a thread rubber layer provided on the outside of the solid center and a cover for covering the thread rubber layer, characterised in that an oil-resistant substance covers the inner rubber portion and in that the inner rubber portion contains an oily substance. A thread wound golf ball as claimed in claim 1 wherein the inner rubber portion is prepared by press-molding a rubber composition comprising about 100 parts by weight of a base rubber and in the range of from 30 to 500 parts by weight of the oily substance. A thread wound golf ball as claimed in claim 2 wherein the base rubber is selected from polybutadiene rubber, natural rubber, ethylene-propylene-diene monomer terpolymer rubber, polynorbornene rubber, a thermoplastic rubber or a mixture of two or more thereof. A thread wound golf ball as claimed in any one of the preceding claims wherein the oily substance is selected from petroleum compounded oil, plasticizer, rubber substitute, alkylbenzene, liquid rubber or a mixture of two or more thereof. A thread wound golf ball as claimed in any one of the preceding claims wherein the oil-resistant substance is selected from ionomer resin, NBR(acrylonitrile-butadiene rubber), chloroprene rubber, urethane rubber, fluorosilicone rubber or a mixture of two or more thereof. A thread wound golf ball as claimed in any one of the preceding claims wherein the oil resistant substance has a thickness in the range of from 0.01 to 5mm. A thread wound golf ball as claimed in any one of the preceding claims wherein the cover covering the thread wound center is made from an ionomer resin or balata.

Inventors: KATO AKIRA, YABUKI YOSHIKAZU, KATO, AKIRA, YABUKI, YOSHIKAZU
Applicants: SUMITOMO RUBBER IND, SUMITOMO RUBBER INDUSTRIES, LTD.
Application year: 1994
Main classification: A63B37
IPC codes: A63B37